U.S. patent number 5,272,204 [Application Number 07/708,720] was granted by the patent office on 1993-12-21 for polymer/polyol composition, processes for making the same and polyurethane therefrom.
This patent grant is currently assigned to Sanyo Chemical Industries, Ltd.. Invention is credited to Keiichi Akimoto, Masahiro Matsuoka, Takeshi Sumita.
United States Patent |
5,272,204 |
Akimoto , et al. |
December 21, 1993 |
**Please see images for:
( Certificate of Correction ) ** |
Polymer/polyol composition, processes for making the same and
polyurethane therefrom
Abstract
Polymer/polyol compositions, obtained by polymerizing an
ethylenically unsaturated monomer in situ in a polyol in the
presence of inner-olefin containing at least 5 carbon atoms, are of
lower viscosity and can provide polyurethanes having improved
properties. Polymer/polyol compositions, obtained by polymerizing
an ethylenically unsaturated monomer, in situ in a polyol in the
presence of an azo compound and a peroxide having a 10 hours
half-life period temperature which is lower by at least 10.degree.
C. than that of the azo compound, have improved stability even at
higher styrene content.
Inventors: |
Akimoto; Keiichi (Osaka,
JP), Sumita; Takeshi (Ohtsu, JP), Matsuoka;
Masahiro (Kyoto, JP) |
Assignee: |
Sanyo Chemical Industries, Ltd.
(Kyoto, JP)
|
Family
ID: |
24846932 |
Appl.
No.: |
07/708,720 |
Filed: |
May 31, 1991 |
Current U.S.
Class: |
524/700; 521/137;
524/714; 524/715; 524/762; 524/773; 524/850; 524/851; 524/853;
524/854; 524/855; 524/858; 524/881; 525/123; 525/131; 525/404;
525/440.072; 525/445 |
Current CPC
Class: |
C08F
2/44 (20130101); C08G 18/63 (20130101); C08G
18/638 (20130101); C08G 2120/00 (20130101); C08G
2101/00 (20130101) |
Current International
Class: |
C08F
2/44 (20060101); C08G 18/00 (20060101); C08G
18/63 (20060101); C08K 005/05 (); C08K 005/06 ();
C08L 075/04 () |
Field of
Search: |
;521/137
;525/123,131,404,440,445
;524/700,714,715,762,773,850,851,853,854,855,858,881 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Welsh; Maurice J.
Assistant Examiner: Sergent; Rabon
Attorney, Agent or Firm: Oblon, Spivak, McClelland, Maier
& Neustadt
Claims
What is claimed as new and desired to be secured by Letters Patent
is:
1. A polymer/polyol composition, when reacted with a polyisocyanate
yields a polyurethane, wherein the polymer of said composition is
formed by polymerizing (1) an ethylenically unsaturated monomer, in
situ in (2) a polyol, in the presence of (3) an inner-olefin
containing 5 to 30 carbon atoms; wherein said ethylenically
unsaturated monomer (1) is different from said olefin (3); said
polyol (2) comprising at least one polyol having a hydroxyl number
of 15-200selected from the group consisting of polyether polyols,
polyester polyols, modified polyols, and polymer/polyols previously
prepared in situ in any of these polyols; and said polymer being
present in an amount of 1-80% based on the weight of said
composition.
2. The composition of claim 1, wherein the amount of said
inner-olefin (3) is 0.5-50% by weight, based on the total weight of
(1), (2) and (3).
3. The composition of claim 1, wherein said monomer (1) is at least
one monomer selected from the group consisting of aromatic
hydrocarbon monomers, unsaturated nitriles, esters of acrylic acid
and esters of methacrylic acid.
4. The composition of claim 1, wherein said monomer comprises at
least one alpha-olefin containing 5-30 carbon atoms.
5. The composition of claim 4, wherein said monomer further
comprises at least one other monomer selected from the group
consisting of aromatic hydrocarbon monomers, unsaturated nitriles,
ethylenically unsaturated carboxylic acids and derivatives thereof,
other aliphatic hydrocarbon monomers, halogen-containing vinyl
monomers, nitrogen-containing vinyl monomers and vinyl-modified
silicones.
6. The composition of claim 5, wherein said monomer comprising
0.5-50% of said alpha-olefin.
7. The composition of claim 1, wherein said ethylenically
unsaturated monomer is an alpha-olefin having 6-30 carbon
atoms.
8. The composition of claim 1, wherein said polyol (2) comprises a
polyether polyol.
9. A process for producing the polymer/polyol composition of claim
1, which comprises polymerizing (1) an ethylenically unsaturated
monomer, in situ in (2) a polyol, in the presence of (3) an
inner-olefin containing 5 to 30 carbon atoms and in the presence of
an initiator, wherein said ethylenically unsaturated monomer (1) is
different from said olefin (3).
10. The process of claim 9, wherein said initiator is at least one
compound selected from the group consisting of azo compounds,
peroxides, persulfates, perborates and persuccinates.
11. The process of claim 9, wherein said initiator comprises an azo
compound, or a combination thereof with a peroxide having a 10
hours half-life period temperature which is lower by at least
10.degree. C. than that of the azo compound.
12. The composition of claim 1, whrein said monomer (1) is at least
one monomer selected from the group consisting of alpha-olefins
containing 5-30 carbon atoms, aromatic hydrocarbon monomers,
unsaturated nitriles, esters of acrylic acid and esters of
methacrylic acid.
13. A process for producing a polyurethane, which comprises
reacting an organic polyisocyanate with an active hydrogen
atom-containing component comprising the polymer/polyol composition
of claim 1.
14. The process of claim 13, wherein the reaction is performed in
the presence of one or more additives.
15. The process of claim 14, wherein one or more additives are
selected from the group consisting of catalysts, blowing agents and
surfactants.
16. The process of claim 13, wherein said polyisocyanate is reacted
with an active hydrogen atom-containing component comprising,
based on the weight of said component,
(i) at least 5% of said polymer/polyol composition;
(ii) 0-95% of at least one other high molecular weight polyol,
having equivalent weight of 200-4,000, selected from the group
consisting of polyether polyols, polyester polyols and modified
polyols; and
(iii) 0-30% of at least one low molecular weight compound
containing at least two active hydrogen atom-containing groups,
said compound having equivalent weight of at least 30 and less than
200, selected from the group consisting of low molecular weight
polyols and amines.
17. A polyurethane, produced by the process of claim 13.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to polymer/polyol compositions that are
suitable for producing polyurethanes. The invention also relates to
methods for making such compositions and polyurethanes
therefrom.
2. Description of the Prior Art
It is known to produce polyurethanes by reacting an organic
polyisocyanate with a polymer/polyol composition, obtained by
polymerizing one or more ethylenically unsaturated monomers (such
as acrylonitrile and/or styrene) in situ in a polyol (such as
polyether polyol).
The viscosity of known polymer/polyol compositions increases in
accordance with an increase in polymer content. The increased
polymer content is required in order to produce polyurethanes of
improved properties, such as compressive hardness. Additionally, in
polymer/polyol compositions containing higher styrene content, the
dispersibility is adversely affected, while higher styrene content
is desirable in order to inhibit scorching of polyurethanes.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide polymer/polyol
compositions, which are of lower viscosity, even at a higher
polymer content.
It is another object of this invention to provide polymer/polyol
compositions, capable of providing polyurethanes having improved
properties, such as compressive hardness.
It is still another object of this invention to provide
polymer/polyol compositions of improved dispersibility even at
higher styrene content.
It is yet another object of the invention to provide polymer/polyol
compositions capable of producing polyurethanes without
scorching.
Briefly, these and other objects of the present invention, which
describes hereinafter will become more readily apparent, have been
attained broadly by providing a polymer/polyol composition,
obtained by polymerizing an ethylenically unsaturated monomer in
situ in a polyol in the presence of an inner-olefin containing at
least 5 carbon atoms, or by polymerizing an ethylenically
unsaturated monomer in situ in a polyol in the presence of
initiators comprising an azo compound and a peroxide having a 10
hours half-life period temperature which is at least 10.degree. C.
lower than that of the azo compound.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As an embodiment of this invention, polymer/polyol compositions can
be produced by polymerizing (1) an ethylenically unsaturated
monomer in situ in (2) a polyol in the presence of (3) an
inner-olefin containing at least 5 carbon atoms.
Suitable inner-olefins (3) include straight-chain and branched
ones, containing usually at least 5, preferably 6-30, more
preferably 8-20, particularly 9-18 carbon atoms and having a double
bond (C.dbd.C) at non-alpha-position (2-, 3-, 4-position and so
on). Branched olefins are preferred. Olefins containing less than 5
carbon atoms have boiling points which are too low; while olefins
containing carbon atoms exceeding 30 result in solidification.
Illustrative of suitable inner-olefins are 2-, 3- and 4- hexenes,
octenes, nonenes, decenes, dodecenes, tetradecenes, hexadecenes,
octadecenes, eicosenes, heneicosenes, docosenes, tricosenes,
tetracosenes, pentacosenes, hexacosenes, and the like, as well as
mixtures of two or more of them. Among these, preferred are
octenes, nonenes, decenes, dodecenes, tetradecenes, hexadecene and
octadecenes; and particularly preferred are nonenes.
Suitable ethylenically unsaturated monomers (1) include, for
example, aromatic hydrocarbon monomers, such as styrene,
alpha-methyl styrene, and the like; unsaturated nitriles, such as
(meth)acrylonitrile [acrylonitrile and methacrylonitrile; similar
expressions are used hereinafter]; and (meth)acrylate esters,
including alkyl (meth)acrylates containing 1-30 or more carbon
atoms in the alkyl group, such as methyl, butyl, nonyl, decyl,
undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,
octadecyl, eicosyl and docohyl (meth)acrylates.
Other examples of suitable ethylenically unsaturated monomers are
alpha-olefins containing usually at least 5 carbon atoms,
preferably 6-30, more preferably 8-20, particularly 11-18 carbon
atoms; and include, for example, 1-hexene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene,
1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene,
1-pentacosene, 1-hexacosene, and the like, as well as mixtures of
two or more of them.
One or more monomers other than above may also be used if
necessary. Suitable examples of such monomers include ethylenically
unsaturated carboxylic acids and derivatives thereof, such as
(meth)acrylic acids, and (meth)acrylamides; aliphatic hydrocarbon
monomers, such as ethylene, propylene and iso-butylene;
fluorine-containing vinyl monomers, such as perfluorooctylethyl
(meth)acrylates; nitrogen-containing vinyl monomers, such as
dialkylaminoethyl (meth)acrylates and morpholinoethyl
(meth)acrylates; vinyl-terminated silicones, and the like.
Among these ethylenically unsaturated monomers (1), preferred are
(i) combinations of alpha-olefin with one or more other monomers,
and (ii) at least one monomer selected from the group consisting of
aromatic hydrocarbon monomers, unsaturated nitriles and
(meth)acrylate esters. More preferred are combinations of
alpha-olefin with at least one monomer selected from the group
consisting of aromatic hydrocarbon monomers, unsaturated nitriles
and (meth)acrylate esters.
In producing polymer/polyols by polymerizing one or more
ethylenically unsaturated monomers (1), the content of aromatic
hydrocarbon monomer is generally 0-90%, preferably 0-80%, based on
the total weight of the monomers (1). Polymer/polyols, obtained by
using more than 90% of styrene, provide polyurethanes of poor
rigidity. The content of unsaturated nitrile is usually 0-99.5%,
preferably 20-55%. Weight ratio of aromatic hydrocarbon
monomer/unsaturated nitrile is usually 0/100-80/20, preferably
44/55-70/30. The content of (meth)acrylate esters is generally
0-50%, preferably 0-30%. Use of more than 50% of (meth)acrylate
esters results in viscous polymer/polyols at higher polymer
content. The amount of monomers other than above is usually 0-30%,
preferably 0-10%. The content of alpha-olefin containing at least 5
carbon atoms is usually 0.5-50%, preferably 1-20%, based on the
total weight of the monomers. When the content of alpha-olefin is
less than 0.5%, the resulting polymer/polyols become viscous at
higher polymer content; and use of more than 50% causes
difficulties in producing polyurethane foams. In the
above-mentioned compositions and hereinafter, % represents percent
by weight (wt %) unless otherwise specified.
Suitable polyols (2) employed for producing polymer/polyol
compositions according to this invention include, for example,
polyether polyols, polyester polyols, and mixtures of them, both of
which polyols are usually used as raw materials for producing
polyurethanes.
Illustrative of such polyether polyols are those obtainable by
addition of alkylene oxide to compounds containing at least two
(preferably two to eight) active hydrogen atoms [such as polyhydric
alcohols, polyhydric phenols, amines, polycarboxylic acids,
phosphoric acids and the like] and mixtures of two or more of such
adducts.
Suitable examples of polyhydric alcohols include diols, for
example, alkylene glycols, such as ethylene glycol, propylene
glycol, 1,3- and 1,4-butane diols, 1,6-hexane diol, neopentyl
glycol, diethylene glycol and the like, and cyclic group-containing
diols, as written in JPN Patent Publication No. 1474/1970, such as
bis(hydroxymethyl) cyclohexane, bis(hydroxyethyl)benzene, and the
like; trihydric alcohols, such as glycerol, trimethylolpropane,
trimethylolethane, hexane triol, triethanol amine, and the like;
tetrahydric alcohols, such as pentaerythritol,
alpha-methylglucoside, diglycerol, and the like; and polyols having
higher functionality (5-8 or higher), for example, sugar alcohols,
including pentitols (such as adnitol, arabitol and xylitol) and
hexitols (such as sorbitol, mannitol, iditol, talitol and
dulcitol), saccharides, including monosaccharides (such as glucose,
mannose, fructose, galactose, allose, altrose, talose, gulose,
idose, sorbose, psicose and tagatose), di- or oligo-saccharides
(such as sucrose, trehalose, cellobiose, lactose and raffinose),
glycosides, such as glucosides of polyols (for instance, glycols,
such as ethylene glycol and propylene glycols, alkane polyols, such
as glycerol, trimethylolpropane, hexane triol and pentaerythritol);
poly(alkane polyol)s (polyglycerols, such as triglycerol and
tetraglycerol, and polypentaerythritols, such as dipentaerythritol
and tripentaerithritol), and cycloalkane polyols, such as
tetrakis(hydroxymethyl)cyclohexanol.
Exemplary of suitable polyhydric phenols are mono-nuclear phenols,
such as hydroquinone, catechol, resorcin, pyrogallol and
phloroglucinol, and poly-nuclear phenols, for example, bisphenols,
such as bisphenol A, bisphenol F, bisphenol sulfon and the like, as
well as phenol-formaldehyde condensation products (novolaks), such
as polyphenols as disclosed in U.S. Pat. No. 3,265,641.
Suitable amines are inclusive of ammonia; alkanol amines, such as
mono-, di- and tri- ethanol amines and isopropanol amines, and
aminoethylethanolamine and the like; aliphatic, aromatic,
araliphatic and alicyclic monoamines, for example, C.sub.1
-C.sub.20 alkyl amines (such as methyl, ethyl, isopropyl, butyl,
octyl and lauryl amines, and the like), aniline, toluidine,
naphthyl amines, benzyl amine, cyclohexyl amine and the like;
aliphatic, aromatic, araliphatic and alicyclic polyamines, such as
C.sub.2 -C.sub.6 alkylene diamines (such as ethylene diamine,
propylene diamine, hexamethylene diamine and the like),
polyalkylene polyamines (such as diethylene triamine, triethylene
tetramine and the like), aromatic diamines (such as tolylene
diamines, phenylene diamines, xylylene diamines, methylene
dianilines, diphenylether diamines and other aromatic polyamines),
alicyclic diamines (such as isophorone diamine, cyclohexylene
diamines, dicyclo-hexylmethane diamines and the like); and
heterocyclic polyamines, such as piperazine,
N-aminoethylpiperazine, and other hetero-cyclic polyamines, written
in JPN Patent Publication No. 21044/1980.
Two or more of these active hydrogen atom-containing compounds may
also be used in conjunction.
Among these active hydrogen atom-containing compounds, preferred
are polyhydric alcolhols. Among polyhydric alcohols, preferred are
ethylene glycol, propylene glycol, glycerol, trimethylol propane,
hexane triol, pentaerythritol, methylglucoside, sorbitol and
sucrose.
Suitable alkylene oxides (hereinafter referred to as AO), employed
for producing polyether polyols, include, for example, ethylene
oxide (hereinafter referred to as EO), propylene oxide (hereinafter
referred to as PO), 1,2-, 2,3- , 1,3- and 1,4-butylene oxides,
styrene oxide, epichlorohydrin and the like, as well as
combinations of two or more of them (block and/or random addition).
Among these, preferred are EO and/or PO, and combination thereof
with smaller amount (such as up to 5% based on the total weight of
AO) of other AO. More preferred are PO and combination of PO with
EO.
Addition of AO to active hydrogen atom-containing compounds can be
carried out in the usual way, with or without catalysts such as
alkaline catalysts, amine catalysts and acidic catalysts, under
normal or elevated pressure, in a single step or multi-stages.
In general, among polyether polyols, preferred are those containing
polyoxypropylene chain, and those containing both polyoxypropylene
and polyoxyethylene chains. Such polyether polyols, include those
obtained by addition of PO to active hydrogen atom-containing
compound(s) as stated above; block adducts obtained by adding PO
and EO to active hydrogen atom-containing compound(s), in such
manners as (1) adding PO followed by EO (tipped), (2) adding
PO-EO-PO-EO in this order (balanced), (3) adding EO-PO-EO in this
order, and (4) adding PO-EO-PO in this order (activated secondary);
random adducts, such as (5) mixed-adding EO/PO; and random/block
adducts, such as (6) adding PO-EO/PO-optionally PO-EO in this
order, as written in JPN Lay-open Patent No. 209920/1982, and (7)
adding EO/PO followed by EO, as described in JPN Lay-open Patent
No. 13700/1978. (In the above, EO/PO means a mixture of EO and PO.)
Smaller amount (for instance, up to 5% based on the total weight of
AO) of other AO (such as butylene oxides, styrene oxide) may be
contained in any of PO and/or EO in the above.
The content of polyoxyethylene chains (hereinafter referred to as
EO content) may be varied widely.
When moderate or slow curability is desirable, EO content is
generally 25% or less, based on the total weight of AO. In case
where rapid curability is required, EO content is usually at least
5%, preferably 7-50%, more preferably 10-40%, in view of
reactivity, curing characteristics, initial physical properties,
compatibility and unform reaction with isocyanates, and
workability. There may be used polyether polyols of EO content less
than 5% in combination with ones of EO content more than 5%, or
ones of EO content more than 50% with ones of EO content less than
50%, so as to provide an average EO content within the above
range.
For rapid curability, particularly preferred are polyols containing
terminal polyoxyethylene chains. Terminal EO content is usually at
least 5%, preferably at least 7, more preferably 7-30%. Internal EO
content is generally at most 50%, preferably 10-40%. The primary
hydroxyl content of such polyols is usually at least 20%,
preferably at least 30%, more preferably at least 50%, most
preferably at least 70%.
Suitable polyester polyols are inclusive of condensation products
of polyols dihydric alcohols (such as ethylene glycol, propylene
glycol, 1,3- and 1,4-butane diols, 1,6-hexane diol, neopentyl
glycol, and diethylene glycol) or combinations thereof with
trihydric or higher functional polyhydric alcohols (such as
glycerol, trimethylolpropane and the like) and/or polyether polyols
(such as those described above) with dicarboxylic acids (for
example, aliphatic or aromatic dicarboxylic acids, such as
glutaric, adipic, sebacic, fumaric, maleic, phthalic and
terephthalic acids) or ester-forming derivatives thereof
(anhydrides and lower alkyl esters, such as maleic and phthalic
anhydrides, dimethyl terephtharate, and the like); and ring-opening
polymerization products of lactones (such as
epsilon-caprolactone).
Instead of or in combination with these polyols (polyether polyols
and/or polyester polyols), modified polyols, for example,
urethane-modified polyols (OH-terminated urethane prepolymers)
prepared from organic polyisocyanates and excess of these polyols,
and polyols containing polymerizable unsaturated bonds in the
molecules (such as maleic anhydride-modified polyols) may also be
employed for producing polymer/polyol compositions in accordance
with this invention.
Among these polyols (2), preferred are polyether polyols.
These polyols (polyether polyols or other high molecular weight
polyols), used for producing polymer/polyol compositions according
to the invention, have usually 2-8 hydroxyl groups, preferably
2.3-4 hydroxyl groups (average). Hydroxyl number (hereinafter
referred to as OHV) of these polyols is usually 200 or less,
preferably 15-100, more preferably 20-70. Polyols having OHV more
than 200 cause difficulty in foaming and result in too rigid and
brittle polyurethanes. Molecular weight of these polyols is usually
2000-30000 or higher, preferably 2500-10000.
These polyols (polyether polyols or other high molecular weight
polyols) can be used as a mixture of those having different OHV,
for instance, a mixture of a major amount (usually at least 50%) of
those having OHV of 70 or less and those having OHV of 80-500.
These high molecular weight polyols may also be used in combination
with a minor amount (for example, 20% or less, particularly 5% or
less) of low molecular weight polyols having high OHV (such as 700
or more). Examples of such low molecular weight polyols include
polyhydric alcohols, as mentioned above as the raw materials for
polyether polyols, as well as low mole AO (such as EO and/or PO)
adducts of active hydrogen atom-containing compounds (such as
polyhydric alcohols, amines and so on, as described above).
In producing polymer/polyol composition, in accordance with this
invention, the amount of said ethylenically unsaturated monomer (1)
is generally 1-80 parts, preferably 5-60 parts, per 100 parts of
the total amount of said polyol (2) and said monomer (1). Using
said monomer above 80 parts results in phase separation into polyol
and polymer phases. Amounts lower than 1 part leads to
polyurethanes of poor physical properties, such as compressive
hardness. In the above-mentioned compositions and hereinafter,
"parts" represents parts by weight unless otherwise specified. The
amount of said inner-olefins (3) contain usually at least 5 carbon
atoms is usually 0.5-50%, preferably 1-20%, based on the total
weight of (1), (2) and (3).
Preparation of polymer/polyol compositions according to this
invention can be carried out in the usual way. Suitable methods
include, for example, those by polymerizing monomer in polyol in
the presence of polymerization initiator (such as radical
generators), as described in U.S. Pat. No. 3,383,351, JPN Patent
Publication Nos. 24737/1964 and 47999/1972 and JPN Lay-open Patent
No. 15894/1975; and those by grafting polymer, prepared from
monomer beforehand, to polyol in the presence of radical generator,
as described in JPN Patent Publication No. 47597/1972. Preferred is
the former method.
Polymerization is usually carried out in the presence of
polymerization initiators. Suitable initiators are free radical
generators, for example, azo compounds, peroxides and others.
Examples of suitable azo compounds include
2,2'-azobisisobutyro-nitrile (hereinafter referred to as AIBN)
{65.degree. C.}, 2,2'-azobis(2,4-dimethylvaleronitrile)
(hereinafter referred to as AVN) {51.degree. C.},
2,2'-azobis(2-methylbutyronitrile {67.degree. C.},
1,1'-azobis(cyclohexane-1-carbonitrile) (hereinafter referred to as
ACCN) {88.degree. C.},
2-phenyl-azo-4-methoxy-2,4-dimethylvaleronitrile {122.degree. C.},
1-[(1-cyano-1methylethyl)azo] formimido(2-carbamoylazo)
iso-butyronitrile {104.degree. C.},
2,2'-azobis(2,4,4-trimethylpentane) azodi-t-octane {110.degree.
C.}, 2,2'-azobis(2methylpropane)azodi-t-butane {160.degree. C.},
dimethyl 2,2-azobis(2-methylpropionate) {66.degree. C.},
2,2'-azobis[2-(hydroxymethyl)] propionitrile {77.degree. C.}, and
the like. Illustrative of suitable peroxides are percarbonates, for
example bis(4-t-butylcyclohexyl) peroxydicarbonate (hereinafter
referred to as TCP) {44.degree. C.}, di-3-methoxybutyl
peroxydicarbonate {43.degree. C.}, di-sec-butyl peroxydicarbonate
{45.degree. C.}, di-isopropyl peroxydicarbonate, t-butyl
peroxyiso-propylcarbonate, and the like; diacyl peroxides, such as
iso-butyryl peroxide (hereinafter referred to as IBP) {33.degree.
C.}, 2,4-dichlorobenzoyl peroxide {54.degree. C.}, lauroyl peroxide
{61.degree. C.}, dibenzoyl peroxide, di-t-butyl peroxide, dicumyl
peroxide, and the like; alkyl peresters, such as t-butyl
peroxyneodecanoate (hereinafter referred to as BPND) {47.degree.
C.}, t-butyl peroxypivalate { 45.degree. C.},
2,5-dimethyl-hexane-d2,5-diper-2-ethylhexoate, t-butyl
peroxy(2-ethyl-hexanoate), t-butyl percrotonate, t-butyl
perisobutyrate, di-t-butyl perphthalate and the like; methyl
isobutyl ketone peroxide, t-butyl hydroperoxide, 1,1-di-t-butyl
peroxy-3,3,5-trimethylcyclohexane and so on; and peroxides other
than above, as written in JPN Ptent Lay-open No. 76517/1986. In the
above, the numerical value within braces { } represents a 10 hours
half-life period temperature, that is the temperature providing
half-life period of 10 hours.
Other initiators include, for instance, persulfates, perborates,
persuccinates and so on. Among these initiators, preferred are azo
compounds (especially AIBN and AVN), peroxides (especially TCP and
BPND), and particularly combinations of them described bellow.
As another embodiment of the present invention, polymer/polyol
compositions are produced by polymerizing said monomer (1) in situ
in said polyol (2) in the presence of initiators comprising (A) an
azo compound and (B) a peroxide having a 10 hours half-life period
temperature which is lower by at least 10.degree. C. than that of
the azo compound. Peroxides preferably have half-life period
temperature not more than 10 seconds. Illustrative examples of such
combinations of initiators are as follows:
__________________________________________________________________________
(A) AIBN AIBN AIBN ACCN ACCN ACCN AVN ACCN ACCN ACCN AIBN AIBN AVN
AIBN AIBN AVN AVN AVN (B) BPND TCP IBP BPND TCP IBP IBP BPND BPND
IBP BPND BPND BPND IBP TCP IBP *, .degree.C. 17 21 32 41 44 55 18
41 55 55 17 21 18
__________________________________________________________________________
*difference of 10 hours halflife period temperatures
The initiators in this invention usually comprises 10-90%
preferably 20-80% of the azo compound, and 10-90% preferably 20-80%
of said peroxide.
In producing polymer/polyol compositions, in accordance with the
invention, the amount of polymerization initiator is usually
0.05-20%, preferably 0.1-15%, more preferably 0.2-10%, based on the
weight of the monomer (1).
Polymerization can be performed in the absence of solvent or
alternatively in the presence of one or more solvents (particularly
in case of producing polymer/polyol compositions of high polymer
content). Suitable solvents include, for example, benzene, toluene,
xylene, acetonitrile, ethyl acetate, hexane, heptane, dioxane,
N,N-dimethylformamide, N,N-dimethylacetoamide, iso-propanol,
n-butanol and the like.
Polymerization may also be carried out in the presence of known
chain transfer agents, if necessary. Illustrative of suitable chain
transfer agents are halogenated hydrocarbons, such as carbon
tetrachloride, carbon tetrabromide and chloroform; alcohols, such
as iso-propanol, methanol, 2-butanol and allyl alcohol; alkyl
mercaptans, such as dodecyl mercaptan and mercaptoethanol; and
enolethers as described in JPN Lay-open Patent No. 31,880/1980.
Polymerization may be performed continuously or batchwise.
Polymerization is carried out at temperature above the
decomposition temperature of the polymerization initiator, usually
at 60.degree.-180.degree. C., preferably at 90.degree.-160.degree.
C., more preferably at 100.degree.-150.degree. C., under
atmospheric pressure, under pressure or under increased reduced
pressure.
Polymer/polyol compositions obtained after polymerization may be
used as raw materials for polyurethane, as such without any
after-treatment; but it is desirable to remove impurities such as
decomposition products of polymerization initiators, unreacted
monomers, organic solvents and so on, by conventional means.
Polymer/polyol compositions thus obtained are translucent or
opaque, white or brownish yellow dispersions, in which all the
polymerized monomers (namely, polymers) are stably dispersed in
polyols.
Polymer content of said polymer/polyol compositions is generally
1-80%, preferably 3-60%, more preferably 5-20%.
OHV of polymer/polyol compositions is generally 5-100, preferably
7-90, more preferably 15-80, most preferably 20-70 mgKOH/g.
In producing polyurethanes from polymer/polyol composition (a),
according to the present invention, one or more other active
hydrogen atom-containing compounds may be used in combination, if
desired. Such compounds include, for example, high molecular
polyols (b) and low molecular weight active hydrogen atom
containing compounds (c), and combinations of (b) and (c).
Examples of suitable high molecular weight polyols (b) are
polyether polyols, polyester polyols, urethane-modified polyols,
and vinyl-modified polyols or polymer/polyols other than (a).
Suitable polyether polyols and polyester polyols include the same
ones as described as the raw materials for polymer/polyol
compositions. Examples of polymer/polyols other than (a) are those
obtainable by polymerizing ethylenically unsaturated monomers such
as those described above (i.e., acrylonitrile and styrene) in situ
in these polyols (such as polyether polyols and/or polyester
polyols, and the like) without using inner-olefins and without
using the particular combinations of initiators as mentioned above,
for instance, those written in JPN Lay-open Patents No. 101899/
1979 and No. 122396/1979. Polyols from natural oils such as castor
oil, modified polyols as mentioned above, polybutadiene polyols and
hydroxyl-containing vinyl polymers (such as acrylic polyols), as
described in JPN Lay-open Patents No. 57413/1983 and No.
57414/1983, for instance, may also be used. Such high molecular
weight polyols (b) usually contain 2-8 or more hydroxyl groups and
have OH equivalent weight of 200-4000, preferably 3-8 hydroxyl
groups and have OH equivalent weight of 400-3000. Among these
polyols (b), preferred are polyether polyols.
Examples of suitable low molecular weight active hydrogen
atom-containing compounds (c) include compounds containing at least
two (preferably 2-3, particularly 2) active hydrogen atoms (such as
hydroxyl, amino and mercapto, preferably hydroxyl) and having a
molecular weight of 500 or less (preferably 60-400) or an
equivalent weight (molecular weight per active hydrogen
atom-containing groups) of at least 30 and less than 200, which
compounds are generally called chain-extenders or crosslinkers.
Such compounds include, for instance, low molecular weight polyols
and aminoalcohols. Illustrative examples of such polyols are
dihydric alcohols, such as ethylene glycol, diethylene glycol,
propylene glycols, dipropylene glycol, 1,3- and 1,4-butane diols,
neopentyl glycol and 1,6-hexane diol; alcohols containing three or
more hydroxyl groups, such as glycerol, trimethylol propane,
pentaerythritol, diglycerol, alpha-methylglucoside, sorbitol,
xylitol, mannitol, dipentaerythritol, glucose, fructose, sucrose
and the like; polyhydroxyl componds having molecular weight of
200-400, obtainable by adding a smaller amount of one or more AO
(such as EO and/or PO) to active hydrogen atom-containing compounds
(such as polyhydric alcohols as mentioned above), for example
polyethylene glycols and polypropylene glycols; cyclic
group-containing diols, as disclosed in JPN Patent Publication
No.1474/1970, for example, AO (such as EO and/or PO) adducts of
polyhydric phenols (such as bisphenol A, hydroquinone and the like;
tertiary or quaternary nitrogen atom-containing polyols, for
instance, those as written in JPN Lay-open Patent No.130699/1979,
N-alkyldialkanol amines (such as N-methyldiethanol amine,
N-butyldiethanol amine and the like and quaternarized products of
these amines), and trialkanol amines (such as triethanol amine,
tripropanol amines and the like); and sulfur-containing polyols,
such as thiodiglycol. Suitable aminoalcohols inculude, for example,
mono- and di-alkanolamines, such as mono- and di- ethanol amines
and propanol amines. Among these, preferred are low molecular
weight polyols (especially diols). More preferred are ethylene
glycol, 1,4-butane diol, neopentyl glycol, 1,6-hexane diol, and
mixtures of two or more of them.
Other high molecular weight polyols (b) and/or low molecular weight
active hydrogen atom-containing compounds (c) may be added to raw
materials (polyether polyols) of polymer/polyol compositions (a)
according to this invention, during production of (a), or after
production of (a).
In producing polyurethanes, using, as active-hydrogen
atom-containing components, polymer/polyol compositions (a)
according to this invention, with or without other high molecular
weight polyols (b) and/or low molecular weight active hydrogen
atom-containing compounds (c), the amount of (a) is usually at
least 5%, preferably at least 10%, more preferably at least 50%,
the amount of (b) is generally 0-95%, preferably 0-80%, more
preferably 0-50%, and the amount of (c) is usually 0-30%,
preferably 0-25%, more preferably 0-10%, based on the total weight
of the active-hydrogen atom-containing components such as (a) and
optionally (b) and/or (c). Use of lower amount of (a) results in
polyurethanes of poor physical properties, such as compressive
hardness. Using larger amount of (c) causes high exotherm, and
results in scorching, or molded articles having a tendency to form
blister in the vicinity of the inlet and being too rigid and
brittle.
In producing polyurethanes according to the invention, there can be
used any of organic polyisocyanates, conventionally employed for
production of polyurethanes. Suitable polyisocyanates include
aromatic polyisocyanates containing 6-20 carbon atoms (except
carbon atoms in NCO groups), aliphatic polyisocyanates containing
2-18 carbon atoms, alicyclic polyisocyanates containing 4-15 carbon
atoms, araliphatic polyisocyanates containing 8-15 carbon atoms,
and modified polyisocyanates of these polyisocyanates containing
urethane, carbodiimide, allophanate, urea, biuret, urethdione,
urethonimine, isocyanurate and/or oxazolidone groups. Illustrative
examples of polyisocyanates are: aromatic polyisocyanates, such as
1,3- and/or 1,4-phenylenediisocyanates, 2,4- and/or
2,6-tolylenediisocyanates (TDI), crude TDI,
diphenylmethane-2,4'-and/or 4,4'-diisocyanates (MDI), crude MDI or
polymethylene-polyphenylenepolyisocyanates (PAPI) obtained by
phosgenation of crude diamino-diphenyl methane, condensation
products of formaldehyde with aromatic amine such as aniline, or a
mixture thereof; mixtures of diamino-diphenyl methane and minor
amount (such as 2-20%) of polyamine of 3 or higher functionality;
naphthalene-1,5-diisocyanate,
triphenylmethane-4,4',4"-triisocyanate, m-and p-isocyanato-phenyl
sulfonyl isocyanate, and the like; aliphatic polyisocyanates, such
as ethylenediisocyanate, tetramethylenediisocyanate,
hexamethylenediisocyanate, dodecamethylenediisocyanate,
1,6,11-undecanediisocyanate, 2,2,4-trimethylhexanediisocyanate,
lysine diisocyanate, 2,6-diisocyanato-methyl caproate,
bis(2-isocyanato-ethyl fumarate, bis(2-isocyanato-ethyl) carbonate,
2-isocyanatoethyl-2,6-diisocyanato-hexanoate, and the like;
alicyclic polyisocyanates, such as isophorone diisocyanate,
dicyclohexylmethane diisocyanates (hydrogenated MDI), cyclohexylene
diisocyanates, methylcyclohexylene diisocyanates (hydrogenated
TDI), bis(2-isocyanato-ethyl) 4-cyclohexene-1,2-dicarboxylate, and
the like; araliphatic polyisocyanates, such as xylylene
diisocyanates, diethylbenzene diisocyanates, and the like; and
modified polyisocyanates of these polyisocyanates, containing
urethane, carbodimide, allophanate, urea, biuret, urethdione,
urethimine, isocyanurate and/or oxazolidone groups, such as
urethane-modified TDI, carbodiimide-modified MDI, urethane-modified
MDI, trihydrocarbyl phosphate-modified MDI, and the like; as well
as mixtures of two or more of them, such as combination of modified
MDI with urethane-modified TDI (isocyanate-terminated prepolymer).
Examples of suitable polyols, used for producing urethane-modified
polyisocyanates (isocyanate-terminated prepolymer obtained from a
polyol with excess polyisocyanate, such as TDI, MDI), are polyols
having equivalent weight of 30-200, for example, glycols, such as
ethylene glycol, propylene glycol, diethylene glycol and
dipropylene glycol; triols, such as trimethylol propane and
glycerol, polyols of higher functionality, such as pentaerythritol
and sorbitol; and AO (EO and/or PO) adducts of them. Among these,
preferred are those having a functionality of 2-3. Free
isocyanatecontent of these modified polyisocyanates and prepolymers
are generally 8-33%, preferably 10-30%, more preferably 12-29%.
Among these polyisocyanates, preferred are aromatic polyisocyanates
and modified ones therefrom. More preferred are TDI (including 2,4-
and 2,6-isomers, mixtures of them and crude TDI) and MDI (including
4,4'- and 2,4'-isomers, mixtures of them and crude MDI or PAPI),
and modified polyisocyanates containing urethane, carbodiimide,
allophanate, urea, biuret and/or isocyanurate groups, derived from
these polyisocyanates (TDI and/or MDI). The most preferred are TDI,
crude MDI and modified MDI.
Polyurethanes, produced from polymer/polyol compositions, in
accordance with the present invention, include foamed or cellular
compositions (foams), and non-cellular compositions (such as
elastomers, sheet materials and so on).
In producing polyurethane foams, foaming can be attained by using
blowing agents, or by introducing gases, such as air (air loading),
or combination of them. Examples of suitable blowing agents are
reactive blowing agents, such as water, which generates carbon
dioxide by reaction with polyisocyanate, and the like; and volatile
blowing agents, for example, halogen-substituted aliphatic
hydrocarbons, such as methylene chloride, chloroform, compressive
hardethylidene dichloride, vinylidene chloride,
trichloro-fluoromethane, dichlorofluoromethane and the like;
low-boiling hydrocarbons, such as butane, hexane, heptane and the
like; and volatile organic solvents without halogen, such as
acetone, ethyl acetate, diethylether and the like; as well as
combinations of two or more of them. Among these, preferred are
halogen-substituted aliphatic hydro-carbons (particularly freons,
such as methylene chloride and trichlorofluoromethane), water and
combinations of them. The amount of blowing agents can be varied
according to the desired density of polyurethanes, which may vary
widely, for instance, from 0.01 to 1.4 g/cm.sup.3.
In producing polyurethanes, according to this invention, organic
polyisocyanates and active hydrogen atom-containing components such
as (a), and optionally (b) and/or (c) and/or water are reacted in
such an amount to provide NCO index of usually 80-140, preferably
85-120, more preferably 95-115, most preferably 100-110.
Furthermore, drastically higher NCO index than the above-mentioned
range, for instance 150-5000 or more, preferably 300-1000, may be
employed to introduce isocyanurate linkages into polyurethanes
(resins or foams).
In producing polyurethanes according to this invention, there may
be used, if necessary, any known materials, such as catalysts, and
other auxiliaries, usually employed in producing polyurethanes.
Examples of suitable catalysts are amine catalysts, including
tertiary amines, secondary amines, alkanolamines and quaternary
ammonium hydroxides, for example, triethylamine, tributylamine,
N-methylmorpholine, N-ethylmorpholine,
N,N,N',N'-tetramethylethylenediamine,
pentamethyldiethylenetriamine, triethylenediamine,
N-methyl-N'-dimethylaminoethyl-piperazine, N,N-dimethylbenzylamine,
N,N-dimethylcyclohexylamine,
N,N,N',N'-tetramethyl-1,3-butanediamine, 1,2-dimethylimidazole,
dimethylamine, N-methyldiethanolamine, N-ethyldiethanolamine,
N,N-dimethylethanolamine, N,N-diethylethanolamine,
tetraalkylammonium hydroxides (such as tetramethylammonium
hydroxide), aralkyltrialkylammonium hydroxides (such as
benzyltrimethylammonium hydroxide), diazabicycloalkenes as
disclosed in U.S. Pat. No. 4,524,104 (such as DBU), and the like;
alkaline catalysts, including phenoxides, hydroxides, alkoxides and
carboxylates of alkali metals (such as sodium and potassium), for
example, sodium phenolate, potassium hydroxide, sodium methoxide,
potassium acetate, sodium acetate, potassium 2-ethylhexanoate and
the like; phosphines, such as triethylphosphine; metal chelete
compounds, such as potassium-salicylaldehyde complex; organotin
compounds, including Sn.sup.II and Sn.sup.IV compounds, such as
stannous acetate, stannous octoate (stannous 2-ethylhexanoate),
dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate,
dibutyltin dilaurate, dibutyltin maleate, dioctyltin diacetate and
the like; other organo metal compounds, such as di-alkyl titanate,
lead naphtenate, and so on. Catalysts for trimerization of NCO
groups forming isocyanurate ring, such as tris(dimethylaminomethyl)
phenol, N,N',N"-tris(di-methylaminopropyl)hexa-hydro-s-triazine and
the like, may also be used. These catalysts are used in small
amounts, for instance, from about 0.001 to about 5% based on the
weight of the reaction mixture.
Exemplary of other auxiliaries are surfactants, as emulsifiers and
foam stabilizers, particularly silicone surfactants
(polysiloxane-polyoxyalkylene copolymers) being important.
Illustrative of other known additives are flame retardants (such as
phosphorus compounds, halogen compounds, Sb.sub.2 O.sub.3 and the
like), retarders (such as acidic compounds), colorants (pigments
and dyes), internal mold release agents (such as hydrocarbon waxes
and silicone compounds), age resistors, antioxidants (such as
hindered phenols), plasticizers, solvents, thixotropants (such as
colloidal silica), germicides, fillers (such as carbon black,
titanium dioxide, diatomaceus earth, glass fiber, shattered glass
fiber, talc, mica, silica, sand, aluminum powder, graphite,
asbestos, and the like), and so on.
Polyurethanes of the present invention can be produced in known
manners, including one-shot process, semi-prepolymer process and
prepolymer process. There may be used any known mixing or foaming
machines usually employed in producing polyurethanes. In case where
no solvent is used, mixing machines, such as kneaders and
extruders, can be used. Production of various non-cellular or
cellular polyurethanes may be carried out in closed mold or open
mold, usually by mixing raw materials with low pressure or high
pressure mixing machines. Other methods, such as spray method, may
also be used. It is preferred to produce polyurethanes by mixing
and reacting using high pressure machines. Furthermore,
polyurethanes may also be produced under vacuum to eliminate gases,
such as air dissolved or mingled in raw materials, before and/or
after mixing, preferably before mixing, of the raw materials.
The present invention is useful for producing high-resilient and
firm, flexible and semi-rigid polyurethane foams, suitable for
energy absorbers, or cushioning materials of automobiles,
furnitures and so on, and for producing cellular and non-cellular
rigid polyurethanes, as well as for producing polyurethanes
suitable for adhesives, coatings and the like.
This invention is particularly useful for producing flexible
polyurethane molded foams and slab foams.
The invention is also useful for producing molded articles by RIM
(reaction injection molding) method. Molding by RIM method can be
carried out in the same conditions as conventional RIM method. For
instance, Component A is prepared by mixing uniformly active
hydrogen atom-containing compounds such as (a) and optionally (b)
and/or (c), and optionally other additives (catalysts, surfactants
and/or other additives), and then optionally adding thereto blowing
agents (water and/or volatile blowing agents) or air loading. As
Component B, polyisocyanate is used. These Components A and B are
charged in the tanks A and B of the high pressure foaming machine.
Components A and B are mixed in the mixing head and introduced into
the mold, via the injection nozzle attached to the mold beforehand.
Molding conditions may be the same as those in the known RIM
methods. For example, the raw materials (2-4 components),
conditioned at a temperature of 25.degree.-90.degree. C., are
intimately mixed in an impingement mixhead under a pressure of
100-200 Kg/cm.sup.2 G and then injected into a closed mold
preheated to a temperature of 30.degree.-200.degree. C. (preferably
60.degree.-90.degree. C.), followed by demolding within 0.1-5
minutes. After demolding, molded articles thus obtained may be
further after-cured or annealed. Annealing can be carried out, for
instance, for 0.3-100 hours at 60.degree.-180.degree. C.,
preferably 80.degree.-160.degree. C., more preferably
100.degree.-150.degree. C., particularly for 1-30 hours at
120.degree.-140.degree. C.
Polymer/polyol compositions, prepared by polymerizing a monomer in
situ in a polyol in the presence of an inner-olefin containing at
least 5 carbon atoms, in accordance with the present invention, are
of lower viscosity even at a higher polymer content, and capable of
providing polyurethanes having improved properties, such as
compressive hardness.
By polymerizing a monomer in situ in a polyol in the presence of
initiators comprising an azo compound and a peroxide having a 10
hours half-life period temperature which is lower by at least
10.degree. C. than that of the azo compound, ratio of
polymerization can be remarkably improved, and there be attained
polymer/polyol compositions having improved dispersibility and are
stable even at higher styrene content, and can provide polyurethane
foams without causing scorching.
Thus, polyurethanes formed from polymer/polyol compositions
according to this invention are particularly useful as automotive
parts, including interior trim and exterior trim, such as handles,
sheet cushion, crash pads, bumpers, fenders, door panels, trunk lid
and outer bodies, as well as elastomeric applications, and
household implements, such as furnitures.
Having generally described the invention, a more complete
understanding can be obtained by reference to certain specific
examples, which are included for purposes of illustration only and
are not intended to be limiting unless otherwise specified.
Raw materials used in the following examples are as follows:
(1)Polyols:
Polyol A: a polyether polyol (OHV:34), produced by addition of PO
to glycerol.
Polyol B: a polyether polyol (OHV: 42, EO content: 10%), produced
by addition of PO to glycerol and sucrose (weight ratio 30/70),
followed by tipping EO.
Polyol C: a polyether polyol (OHV: 55), produced by addition of PO
to glycerol. EG: ethylene glycol.
(2) Ethylenically unsaturated monomers:
D-124: alpha-olefin (C12/C14 weight ratio 56:44). AN:
acrylonitrile, ST: styrene.
(3) Inner-olefin:
Nonene (produced by Arco Chemical).
(4) Polyisocyanate:
TDI-80: TDI (2,4-/2,6-ratio: 80/20)
(6) Catalysts:
DABCO33LV: 33% solution of triethylene diamine in dipropylene
glycol
U-28: tin catalyst (Neostan U-28, produced by Nitro Kasei K.
K.)
(7) Silicone surfactants
L-520: polyether-polysiloxane block copolymer, produced by Nippon
Uncar K. K.
Dispersion stability test of polymer/polyol composition was
measured as follows:
Each polymer/polyol composition was centrifuged for 30 minutes at
about 18,000 rpm with a centrifugal force of about 38,000 g,
followed by turning the centrifuge tube upside down and allowing to
stand for an hour. The weight % of the residue remained within the
centrifuge tube, based on the weight of the initial polymer/polyol
composition, was used as index of dispersion stability.
Measuring methods of properties of polyurethane foams or articles
are as follows.
Density (kg/m.sup.3), Tensile strength (kg/cm.sup.2), Elongation at
break (%), and Tear strength (kg/cm): JIS K-6301. 25% and 65% ILD
(kg/314 cm.sup.2), Rebound elasticity (%), and Compression set (%):
JIS K-6382.
EXAMPLES I TO XVII, AND COMPARATIVE EXAMPLE i TO vii
According to formulations (parts) and polymerization conditions
(temperature, .degree.C., and time, hours) written in Tables 1, 2
and 3, polyols were charged into a reaction vessel equipped with a
stirrer and temperature control means, and heated under stirring.
Then, monomers, initiators and dodecyl mercaptan (hereinafter
referred to as DM) were continuously fed by pump over 2 hours,
while maintaining the temperature, followed by stirring at the same
temperature. Finally, volatile materials were removed under heating
to 110.degree. C. at reduced pressure of 25 mmHg for 3 hours to
obtain polymer/polyol compositions of Examples I to XVII and those
of Comparative Examples i to vii (hereinafter referred to as
P/Polyols I to XVII and P/Polyols i to vii, respectively). OH-V (mg
KOH/g), viscosity (cps. at 25.degree. C.) and stability (%) of
these polymer polyols were measured. The results were as shown in
Tables 1, 2 and 3.
TABLE 1 ______________________________________ Example Example
Comparative Example No. I II III IV i ii iii iv
______________________________________ Polyol B 38.5 38.5 38.5 38.5
38.5 38.5 38.5 38.5 Polyol C 16.5 16.5 16.5 16.5 16.5 16.5 16.5
16.5 AN 15.8 15.8 15.8 15.8 15.8 15.8 15.8 15.8 ST 29.2 29.2 29.2
29.2 29.2 29.2 29.2 29.2 D-124 2.5 -- -- -- -- -- -- 2.5 Nonene 3.0
3.0 5.0 -- -- -- -- -- Dodecene -- -- -- 5.0 -- -- -- -- Hexane --
-- -- -- -- 5.0 -- -- IPA -- -- -- -- -- -- 5.0 5.0 TCP 0.3 0.3 0.3
0.3 0.3 0.3 0.3 0.3 DM 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Temperature
120 120 120 120 120 120 120 120 Time 3.5 3.5 3.5 3.5 3.5 3.5 3.5
3.5 Viscosity 2900 3600 3500 4000 Solid 7500 9000 6800
______________________________________ (Note) IPA: isopropyl
alcohol; DM: dodecyl mercaptan
TABLE 2 ______________________________________ Comparative Example
Example Example No. v vi vii V VI VII VIII IX
______________________________________ Polyol A 19.5 19.5 19.5 19.5
19.5 -- -- Polyol B 45.5 45.5 45.5 45.5 45.5 38.5 38.5 38.5 Polyol
C -- -- -- -- -- 16.5 16.5 16.5 AN 17.5 17.5 17.5 17.5 17.5 22.5
15.8 20.0 ST 17.5 17.5 17.5 17.5 17.5 22.5 29.2 30.0 D-124 -- 2.0
5.0 -- 2.0 2.5 2.5 2.5 Nonene -- -- -- 5.0 3.0 3.0 3.0 3.0 AIBN 0.7
0.7 0.7 0.7 0.7 0.9 1.4 2.3 DM 0.35 0.35 0.35 0.35 0.35 0.2 0.2 0.3
Temperature 125 125 125 125 125 120 120 120 Time 2.5 2.5 2.5 2.5
2.5 3.5 3.5 4.0 Viscosity 7000 4100 2000 2100 1200 3500 3100 5000
______________________________________
TABLE 3
__________________________________________________________________________
Example No. X XI XII XIII XIV XV XVI XVII
__________________________________________________________________________
Polyol B 56.0 56.0 56.0 56.0 56.0 56.0 56.0 49.0 Polyol C 24.0 24.0
24.0 24.0 24.0 24.0 24.0 21.0 AN 7.0 7.0 7.0 7.0 7.0 7.0 7.0 10.5
ST 13.0 13.0 13.0 13.0 13.0 13.0 13.0 19.5 Nonene 3.0 3.0 3.0 3.0
3.0 -- -- -- IBP -- -- -- 0.1 -- 0.05 -- 0.11 BPND -- 0.1 -- -- 0.1
0.05 0.08 -- TCP -- -- 0.1 -- -- -- -- -- AVN -- -- -- 0.1 0.05 --
-- 0.06 AIBN 1.0 0.1 0.1 -- 0.05 0.05 0.03 -- ACCN -- -- -- -- --
0.05 0.09 0.14 Temperature 130 120 110 100 110 100 120 120 Time 1.0
1.0 1.0 1.0 1.0 3.0 1/4 1/4 Ratio of 90.5 97.5 95.7 96.5 98.5 98.5
99.4 99.0 polymerization, % Stability 6.3 3.8 4.1 4.6 4.4 4.5 2.8
3.5 Viscosity 2400 2500 2300 2400 2000 2200 2700 3300
__________________________________________________________________________
EXAMPLES 1 to 9, AND COMPARATIVE EXAMPLES 1 AND 2
Polyurethane foams were produced according to foaming formulations
(parts), written in Tables 4 and 5.
Properties and density (kg/m.sup.3, JIS K-6301) of the resulting
foams were measured, and the results were shown in Tables 4 and
5.
TABLE 4
__________________________________________________________________________
Comparative Example Example Example No. 1 2 1 2 3 4 5
__________________________________________________________________________
Polyol C 100 50 500 0 50 50 50 P/Polyol I 0 0 50 100 0 0 0 P/Polyol
iv 0 50 0 0 0 0 0 P/Polyol VI 0 0 0 0 50 0 0 P/Polyol VII 0 0 0 0 0
50 0 P/Polyol VIII 0 0 0 0 0 0 50 Water 4.5 4.5 4.5 4.5 4.5 4.5 4.5
DABCO 33LV 0.3 0.3 0.3 0.3 0.3 0.3 0.3 U-28 0.30 0.26 0.26 0.22
0.28 0.28 0.26 L-520 1.5 1.5 1.5 1.5 1.5 1.5 1.5 TDI-80 54.6 52.2
52.2 49.7 50.8 52.2 52.2 Density 23.7 26.1 23.8 24.6 26.0 25.6 26.0
25% ILD 10.6 16.4 17.0 28.9 16.8 18.0 17.1 Tensile 1.06 1.21 1.27
1.47 1.16 1.24 1.24 strength Tear 0.87 0.67 0.89 0.85 0.71 0.68
0.65 strength Elongation 174 100 103 58 106 102 100 at break
Rebound 40 34 34 29 35 33 34 elasticity Compression 3.2 6.4 6.5
35.0 8.7 5.9 5.8 set
__________________________________________________________________________
TABLE 5 ______________________________________ Example No. 6 7 8 9
______________________________________ P/Polyol X 100 0 0 0
P/Polyol XI 0 100 0 0 P/Polyol XII 0 0 100 0 P/Polyol XVI 0 0 0 100
Water 4.5 4.5 4.5 4.5 DABCO 33LV 0.3 0.3 0.3 0.3 U-28 0.3 0.3 0.3
0.3 L-520 1.5 1.5 1.5 1.5 TDI-80 52.2 52.2 52.2 52.2 Density 23.6
23.3 23.4 23.5 25% ILD 16.8 17.9 18.5 21.0 Tensile strength 0.86
0.99 1.05 1.12 Tear strength 0.84 0.86 0.90 0.95 Elongation at
break 120 120 125 122 Rebound elasticity 35 34 35 35 Compression
set 5.8 5.8 5.9 6.2 ______________________________________
* * * * *